Synergistic effect of lanthanum-modified bentonite and Vallisneria spiralis on antimony immobilization in aquatic environments

Abstract

Remediation of sedimentary antimony (Sb) in lakes is highly challenging due to its strong sensitivity to alterations in the sediment microenvironment caused by climate changes and anthropogenic activities. This study monitored Sb dynamics at the sediment-water interface through high-resolution sampling. The feasibility of using Lanthanum-modified bentonite (LMB) and Vallisneria spiralis (V. spiralis) for remediating sedimentary Sb was assessed, and the dual mechanisms underlying their remediation effects were elucidated. The results showed that both LMB and V. spiralis successfully inhibited the conversion of sedimentary Sb to the soluble state individually, while their combination was the most effective, with the highest reduction of 60.21%. Specifically, LMB reduced soluble Sb in sediments through electrostatic adsorption of bentonite and inner-sphere complexation of La³⁺ with Sb. V. spiralis primarily enhanced the transformation of mobile Sb into more stable forms to control Sb release. Compared to individual treatments, the combined use of LMB and V. spiralis produced an additive effect, promoting the adsorption of Sb by more in-situ formed Fe(III)/Mn(IV) (hydr)oxides. This further drove ligand exchange and intra-sphere complexation between La³⁺ and Sb, thereby enhancing the adsorption capacity for Sb. The results emphasize the potential of LMB and V. spiralis for Sb passivation in sediments and provide implications for the control of similar contaminants in aquatic environments.

Graphical abstract

Keywords

Lanthanum-modified bentonite / Vallisneria spiralis / Sediment / Soluble antimony (Sb) / Immobilization

Highlight

	● La-modified bentonite effectively immobilizes Sb(V) in aquatic environments.
	● Vallisneria spiralis enhances Sb removal through plant-microbe interactions.
	● The synergistic effect reduces antimony bioavailability in sediments.
	● Combination shows potential in long-term Sb immobilization.

References

[1] Bregoli L , Chiarini F , Gambarelli A , Sighinolfi G , Gatti A M , Santi P , Martelli A M , Cocco L . (2009). Toxicity of antimony trioxide nanoparticles on human hematopoietic progenitor cells and comparison to cell lines. Toxicology, 262(2): 121–129

[2] Chen X , Liu L , Yan W M , Li M J , Guo Z Y , Li Q , He X Y , Zhao Z Y , Liu R Y , Zhang S T . et al. (2022). Effect of lanthanum modified bentonite capping on control of sediment phosphorus and tungsten release. Ecological Engineering, 185: 106788

[3] Cui J Z , Wang D , Lin J , Wang Y , Ren M Y , Yang Y W , Shi P L . (2021). New application of lanthanum-modified bentonite (Phoslock^®) for immobilization of arsenic in sediments. Environmental Science and Pollution Research, 28(2): 2052–2062

[4] Deng J M , Nie W , Huang X , Ding A J , Qin B Q , Fu C B . (2023). Atmospheric reactive nitrogen deposition from 2010 to 2021 in Lake Taihu and the effects on phytoplankton. Environmental Science & Technology, 57(21): 8075–8084

[5] Dong L , Wang X , Tong H , Lv Y , Chen M , Li J , Liu C . (2024). Distribution and correlation of iron oxidizers and carbon-fixing microbial communities in natural wetlands. Science of the Total Environment, 912: 168719

[6] Eltaweil A S , Ibrahim K , Abd El-Monaem E M , El-Subruiti G M , Omer A M . (2023). Phosphate removal by Lanthanum-doped aminated graphene oxide@aminated chitosan microspheres: insights into the adsorption mechanism. Journal of Cleaner Production, 385: 135640

[7] Filella M , Belzile N , Chen Y W . (2002). Antimony in the environment: a review focused on natural waters: I. Occurrence. Earth-Science Reviews, 57(1−2): 125–176

[8] Gao L , Lu J , Xu D Y , Wan X H , Gao B . (2022). Partitioning behavior and ecological risk of arsenic and antimony in the sediment-porewater profile system in the Three Gorges Reservoir, China. Chemosphere, 300: 134409

[9] Gao M R , Sun Q , Wang J H , Ding S M . (2021). Investigation of the combined use of capping and oxidizing agents in the immobilization of arsenic in sediments. Science of the Total Environment, 782: 146930

[10] Güneşli K , Chételat J , Palmer M J , Paudyn K , Astles B , Jamieson H . (2025). Internal loading of antimony from mining contaminated sediments under oxic conditions. Applied Geochemistry, 179: 106272

[11] Guo T Y , Lin J W , Zhan Y H . (2024). Suppression of phosphorus release from sediment by Vallisneria natans combined with iron- and zirconium-modified bentonites: effectiveness, mechanism, and response of sedimentary microbial communities. Journal of Environmental Chemical Engineering, 12(5): 113690

[12] Han Y Q , Jeppesen E , Lürling M , Zhang Y , Ma T T , Li W , Chen K Q , Li K Y . (2022). Combining lanthanum-modified bentonite (LMB) and submerged macrophytes alleviates water quality deterioration in the presence of omni-benthivorous fish. Journal of Environmental Management, 314: 115036

[13] Hao C M , Sun Q Q , Sun X M , Li Q . (2024). Novel insights into antimony mobilization in different high- antimony aquifers from the molecular signatures of dissolved organic matter. Ecotoxicology and Environmental Safety, 277: 116377

[14] He Y N , Sun R Y , Zhang D F , Wang Y , Zhou S X , Deng X J , Wang B L , Hu G Z . (2023). Separable alginate gel spheres encapsulated with La-Fe modified biochar for efficient adsorption of Sb(III) with high capacity. Journal of Hazardous Materials, 460: 132322

[15] Hosseinpour Moghaddam M , Karimian N , Johnston S G , Choppala G , Rastegari M , Burton E D . (2024). Antimony(V) sorption and coprecipitation with ferrihydrite: an examination of retention mechanisms and the selectivity of commonly-applied extraction procedures. Journal of Hazardous Materials, 480: 136297

[16] Hu Z HLi Z YXu YHe F FZhang J NLi T (2025). MgFe-LDHs/Vallisneria natans combined system for simultaneous elimination of endogenous N and P pollution in eutrophic water: performance, synergetic mechanism, and metagenomics analysis. Environmental Research, 279(Pt 1): 121798

[17] Johnston S G , Bennett W W , Doriean N , Hockmann K , Karimian N , Burton E D . (2020). Antimony and arsenic speciation, redox-cycling and contrasting mobility in a mining-impacted river system. Science of the Total Environment, 710: 136354

[18] Kharazian P , Fernández-Ondoño E , Jiménez M N , Sierra Aragón M , Aguirre-Arcos A , Bacchetta G , Cappai G , De Giudici G . (2022). Pinus halepensis in contaminated mining sites: study of the transfer of metals in the plant-soil system using the BCR procedure. Toxics, 10(12): 728

[19] Kong M , Liu F F , Tao Y , Wang P F , Wang C , Zhang Y M . (2020). First attempt for in situ capping with lanthanum modified bentonite (LMB) on the immobilization and transformation of organic phosphorus at the sediment-water interface. Science of the Total Environment, 741: 140342

[20] Kong M , Ouyang X Y , Han T L , Wang W Z , Yin H B , Wang Y . (2024). Combination of lanthanum-modified attapulgite and Vallisneria natans for immobilization of phosphorus in various types of sediments. Chemical Engineering Journal, 492: 152264

[21] Lei H F , Tam N F Y , Geng X H , Zhong M L , Lao X L , Su X T , Huang X X , Wei L Z , Liu Y , Wu Q H . et al. (2024). Adsorption performance of chitosan and glutaraldehyde modified biochars for trivalent antimony in acidic wastewater. Water, Air, & Soil Pollution, 235(8): 503

[22] Li CDing S MChen M SSun QZhang YMa XZhong Z LTsang D C WWang Y (2022a). Mechanistic insights into trace metal mobilization at the micro-scale in the rhizosphere of Vallisneria spiralis. Science of the Total Environment, 806(Pt 3): 150735

[23] Li H B , Wei Y F , Wang Y W , Zhao Y W , Wang L , Feng J T , Sun F . (2024a). Cooperative adsorption of Sb(V) in water by magnetic MgFe₂O₄-biochar composite beads. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 684: 133133

[24] Li Q , He Y , Yang A J , Hu X , Liu F , Mu J C , Mei S X , Yang L P . (2023a). Antimony(III) removal by biogenic manganese oxides formed by Pseudomonas aeruginosa PA-1: kinetics and mecha-nisms. Environmental Science and Pollution Research, 30(43): 97102–97114

[25] Li Q , Liao L , Xu R , Wu Z G , Yin Z , Han Y Q , Zhang Y , Yang Y B , Jiang T . (2023b). In situ preparation of a multifunctional adsorbent by optimizing the Fe²⁺/Fe³⁺/Mn²⁺/HA ratio for simul-taneous and efficient removal of Cd(II), Pb(II), Cu(II), Zn(II), As(III), Sb(III), As(V) and Sb(V) from aqueous environment: behaviors and mechanisms. Journal of Hazardous Materials, 444: 130389

[26] Li Q , Ma X Y , Qi C S , Li R , Zhang W , Li J S , Shen J Y , Sun X Y . (2022b). Facile preparation of novel magnetic mesoporous Fe-Mn binary oxides from Mn encapsulated carboxymethyl cellulose-Fe(III) hydrogel for antimony removal from water. Science of the Total Environment, 821: 153529

[27] Li Q , Yan W M , Li M J , Chen X , Wu T F , He X Y , Yao Q , Yan Y L , Li G X . (2024b). Contrasting effects of a traditional material of polyaluminum chloride and an emerging material of lanthanum carbonate capping on sediment internal phosphorus immobi-lization. Science of the Total Environment, 917: 170538

[28] Li Y H , Gregory S . (1974). Diffusion of ions in sea water and in deep-sea sediments. Geochimica et Cosmochimica Acta, 38(5): 703–714

[29] Limmer M A , Evans A E , Seyfferth A L . (2021). A new method to capture the spatial and temporal heterogeneity of aquatic plant iron root plaque in situ. Environmental Science & Technology, 55(2): 912–918

[30] Lin J , Liu M L , Zhuang S L , Geng B , Wang X D , Ma J S , Chen M S . (2023). Effects on the migration and speciation of heavy metals by combined capping and biochemical oxidation during sediment remediation. Science of the Total Environment, 871: 162055

[31] Liu Z H , Chen M S , Song L L . (2025). Mechanisms of antimony transport in sediment-water systems on an annual scale. Water Research, 287: 124367

[32] Lu Y Q , Ran M D , Jiao Y , Wu J X , Li J K . (2024). Synergistic interplay of selenium (Se) and antimony (Sb)-oxidizing bacteria Bacillus sp. S3 alleviates the Sb toxicity in pak choi (Brassica chinensis L.) by limiting Sb uptake, enhancing antioxidant systems and regulating key metabolic pathways. Environmental and Experimental Botany, 218: 105601

[33] Luo Q Y , Wei J , Guo Z , Song Y H . (2024). Adsorption and immobilization of phosphorus from water and sediments using a lanthanum-modified natural zeolite: performance, mechanism and effect. Separation and Purification Technology, 329: 125187

[34] Mierzwa J , Mumbi R , Ray A , Rakshit S , Essington M E , Sarkar D . (2021). Antimony (V) adsorption at the hematite-water interface: a macroscopic and in situ ATR-FTIR study. Soil Systems, 5(1): 20

[35] Morini L , Ferrari C , Bartoli M , Zilius M , Broman E , Visioli G . (2024). Vallisneria spiralis L. adaptive capacity improves pore water chemistry and increases potential nitrification in organic polluted sediments. Ecological Processes, 13(1): 26

[36] Ouyang E M , Xiang H R , Zhao R , Yang H W , He W Y , Zhang R Y . (2024). Structural design of La₂(CO₃)₃ loaded magnetic biochar for selective removal of phosphorus from wastewater. Environmental Pollution, 345: 123510

[37] Papaslioti E M , Tabuteau H , Farasin J , Vantelon D , Magnin V , Charlet L . (2025). Antimony retention and transformation: a novel approach using microfluidics and hydrogel, biocomposite nanomagnetite aggregates. Environmental Nanotechnology, Monitoring & Management, 23: 101083

[38] Qi P F , Pichler T . (2016). Sequential and simultaneous adsorption of Sb(III) and Sb(V) on ferrihydrite: implications for oxidation and competition. Chemosphere, 145: 55–60

[39] Qiu X S , Chen M Q , Wu P X , Li Y H , Sun L Y , Shang Z B , Wang T M , Dang Z , Zhu N W . (2024). Influence of dissolved organic matter with different molecular weight from chicken manure on ferrihydrite adsorption and re-release of antimony(V). Journal of Environmental Management, 358: 120883

[40] Ren M Y , Ding S M , Fu Z , Yang L Y , Tang W Y , Tsang D C W , Wang D , Wang Y . (2019). Seasonal antimony pollution caused by high mobility of antimony in sediments: in situ evidence and mechanical interpretation. Journal of Hazardous Materials, 367: 427–436

[41] Shan S J , Huang X N , Yang Z Y , Ji J , Chen Z H , Wang C M , Xu X P , Li X , Xu Y , Liu S Q . et al. (2025). Enhanced scavenging and recovery of low-concentration phosphate from secondary effluents using lanthanum-incorporated layered double hydroxide composites. Process Safety and Environmental Protection, 199: 107224

[42] Sundar S , Chakravarty J . (2010). Antimony toxicity. International Journal of Environmental Research and Public Health, 7(12): 4267–4277

[43] Tilahun S , Kifle D . (2021). Atmospheric dry fallout of macronutrients in a semi-arid region: an overlooked source of eutrophication for shallow lakes with large catchment to lake surface area ratio. Earth Systems and Environment, 5(2): 473–480

[44] Tu C Q , Dong X S , Yang H R , Chang Y S , Xu Z S , Che F F , Wang S H , Huang W . (2024). Characterization of phosphate solubilizing bacteria in the sediments of eutrophic lakes and their potential for cyanobacterial recruitment. Chemosphere, 352: 141276

[45] Verma M , Sachan D , Kumar V , Ahmad W , Sharma N , Kim H . (2025). Highly recyclable EDTA-crosslinked chitosan-gelatin biopolymer adsorbent for separation and recovery of rare earth elements from aqueous solution. Frontiers of Environmental Science & Engineering, 19(4): 51

[46] Wang G B , Feng Z K , Yin X R , Chen D J , Zhao N , Yuan Y Q , Chen C Y , Liu C , Ao M , Chen L . et al. (2024). Biogenic manganese oxides promote metal(loid) remediation by shaping microbial communities in biological aqua crust. Water Research, 253: 121287

[47] Wang H Y , Kumar A , Li J , Chen P , Yu Z G , Sun G X . (2023). The adsorption behavior and mechanism for arsenate by lanthanum-loaded biochar with different modification methods. Environ-mental Technology & Innovation, 32: 103344

[48] Wang N N , Zhang S H , He M C . (2018). Bacterial community profile of contaminated soils in a typical antimony mining site. Environmental Science and Pollution Research, 25(1): 141–152

[49] Wang Y Z , Sun X X , Cao Y B , Xu Z M , Sun H C , Guan X J , Ghani M U , Zheng L , Li B Q , Huang D Y . et al. (2025). Identification of hydrogen oxidation coupled with antimonate reduction, a novel antimony biogeochemical cycling, in two contrasting antimony-contaminated environments. Microbiome, 13(1): 152

[50] Wen B , Zhou J W , Tang P D , Jia X C , Zhou W Q , Huang J B . (2023). Antimony (Sb) isotopic signature in water systems from the world's largest Sb mine, central China: novel insights to trace Sb source and mobilization. Journal of Hazardous Materials, 446: 130622

[51] Wu Z H , Zhao Y , Zheng Y , Yin M X , Wang J H , Bolan N , Fan F Y , Yun Z C , Zhou C Z , Yin H L . et al. (2024). The fate of Sb(V) and As(V) during the aging of ferrihydrite. Chemical Engineering Journal, 479: 147671

[52] Xiang Z Q , Huang C K , Huang J C , Yan Y , Liu G B , Yu X M , Liu W J , Cao H J , Liu A Z . (2024). Mechanism for the synergistic removal of Sb(Ⅲ) and Sb(V) from printing and dyeing wastewater by polyferric sulfate. Journal of Environmental Chemical Engineering, 12(2): 112492

[53] Xie X F , Gu S Y , Hao L K , Zhang T Y , Guo Z D . (2022). Rhizosphere microbial communities and geochemical con-straining mechanism of antimony mine waste-adapted plants in Southwestern China. Microorganisms, 10(8): 1507

[54] Yan W MHe X YWu T FChen M SLin JChen XLi QLi M JYan Y LYao Q (2023). A combined study on Vallisneria spiralis and lanthanum modified bentonite to immobilize arsenic in sediments. Environmental Research, 216(Pt 3): 114689

[55] Yang D X , Fang W . (2025). Reduction of antimony bioavailability with the application of stable exogenous organic matter: a comparative study between rice straw and manure compost. Environmental Research, 277: 121578

[56] Yang K L , Zhou J S , Lou Z M , Zhou X R , Liu Y L , Li Y Z , Ali Baig S , Xu X H . (2018). Removal of Sb(V) from aqueous solutions using Fe-Mn binary oxides: the influence of iron oxides forms and the role of manganese oxides. Chemical Engineering Journal, 354: 577–588

[57] Yao B , Li Y X , Zeng W Q , Yang G , Zeng J H , Nie J , Zhou Y Y . (2023). Synergistic adsorption and oxidation of trivalent antimony from groundwater using biochar supported magnesium ferrite: performances and mechanisms. Environmental Pollution, 323: 121318

[58] Yao C , Che F F , Jiang X , Wu Z H , Chen J Y , Wang K . (2021). Study on antimony mobility in a contaminated shallow lake sediment using the diffusive gradients in thin films technique. Chemosphere, 267: 128913

[59] Yu YYu Z LJiang J GWu L FFeng H Y (2023). Assessing the impacts of fine sediment removal on endogenous pollution release and microbial community structure in the shallow lakes. Science of the Total Environment, 897: 165410

[60] Zeng Q Y , Li J H , Dai L M , Zhang J X , Zeng T Y , Cheng R , Chen J , Zhou M , Hou H B . (2024). Synthesis of hydrophilic sulfur-doped carbon aerogel microspheres and their mechanism of efficient removal of Sb(III) from aqueous solution. Separation and Purification Technology, 329: 125032

[61] Zhang C P , Liu T , Yang Z Y , Wu P , Zhang K X , Chen S . (2022). Study on antimony and arsenic cycling, transformation and contrasting mobility in river-type reservoir. Applied Geo-chemistry, 136: 105132

[62] Zhang C Q , Wu M Y , Wu K , Li H S , Zhang G S . (2023a). Efficient removal of antimonate and antimonite by a novel lanthanum-manganese binary oxide: performance and mechanism. Journal of Hazardous Materials, 442: 130132

[63] Zhang G M , He H , Liu S Q , Du Z P , Lv L Y , Sun L , Zhang J , Liang J S . (2024a). La-Al modified Fe₃O₄ adsorbent for adsorption performance and mechanism of low P concentration in water. Journal of Water Process Engineering, 68: 106344

[64] Zhang H X , Huo S L , Yeager K M , Xi B D , Zhang J T , He Z S , Ma C Z , Wu F C . (2018). Accumulation of arsenic, mercury and heavy metals in lacustrine sediment in relation to eutrophication: impacts of sources and climate change. Ecological Indicators, 93: 771–780

[65] Zhang M , Xiong J , Zhou L , Li J J , Fan J Q , Li X , Zhang T , Yin Z Z , Yin H Q , Liu X D . et al. (2023b). Community ecological study on the reduction of soil antimony bioavailability by SRB-based remediation technologies. Journal of Hazardous Materials, 459: 132256

[66] Zhang M X , Zhang Y P , Chen X , Sun J , Lu X W , He Y , Wang Y J . (2023c). Characteristics and mechanism of phosphate removal by lanthanum modified bentonite in the presence of dissolved organic matter. Chemosphere, 340: 139957

[67] Zhang S H , Wu W F , Hu X B , Tang G , Liu Y Y , Zhou B J . (2025). Lanthanum hydroxide-modified zeolite as adsorbents for efficient ammonia nitrogen and phosphate removal and its application in sludge fermentation liquid. Journal of Environmental Chemical Engineering, 13(3): 116779

[68] Zhang X M , Zhen W , Cui S Z , Wang S , Chen W Q , Zhou Q , Jeppesen E , Liu Z W . (2024b). The effects of different doses of lanthanum-modified bentonite in combination with a submerged macrophyte (Vallisneria denseserrulata) on phosphorus inactivation and macrophyte growth: a mesocosm study. Journal of Environmental Management, 352: 120053

[69] Zhang X M , Zhen W , Jensen H S , Reitzel K , Jeppesen E , Liu ZW . (2021). The combined effects of macrophytes (Vallisneria denseserrulata) and a lanthanum-modified bentonite on water quality of shallow eutrophic lakes: a mesocosm study. Environ-mental Pollution, 277: 116720

[70] Zhao C X , Liu Y L , Yan Z X , Zhao W B , Sun J Y . (2024). Combining effects of submerged macrophytes and lanthanum-modified bentonite on sediment enzyme activity: Evidence from mesocosm study. Chemosphere, 364: 143002

[71] Zheng J H , Liu L , Li Q , Zhao P W , Liao Q , Li Q Z , Yang Z H , Si M Y , Ping Y , Xu H . et al. (2025). In situ stabilization of antimony and arsenic in co-contaminated soil using organic matter-Fe/Mn (hydr)oxides colloids and their mineral phase transformation. Journal of Environmental Sciences, 156: 835–848

[72] Zhu L J , Zhang Y , Xu S , Shi B Y , Hao H T , Wang Y L . (2025). Lanthanum hydroxide showed best application potential in La-based materials based on its stable phosphate adsorption properties in complex water environments. Journal of Environ-mental Sciences, 152: 465–476

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